Unilateral Nuclear Magnetic Resonance Research Articles

Fast non-destructive measurement of intramuscular fat in Australian beef and lamb using nuclear magnetic resonance (NMR) technologies

Nuclear magnetic resonance (NMR) is an excellent technique for non-destructive analysis of meat because it has high accuracy, a linear response, and insignificant drift over time, which removes the need for recalibration. Furthermore, single-side NMR devices have open geometries that enable measurements of subsections of larger samples without taking sub-samples. Here we demonstrated long-term reproducibility in a benchtop device and the utility of a single-sided NMR device. We validated long-term reproducibility of NMR measurements of lamb intramuscular fat (IMF%) in a commercial processor boning room years after the original model was created. It was hypothesised that the NMR IMF% model would retain precision and accuracy on independent validation. The root mean squared (RMS) error of prediction of lamb IMF was 0.79 %. The R2 between reference measurements, predicted IMF% was 0.74, the slope of the chemical IMF% vs NMR predictions was 0.989, and the bias was 0.53 % IMF%. In the second example, we showed that IMF% measurements of high value beef striploins could be measured off a commercial processing belt and returned without damaging the product. It was hypothesised that a commercial prototype single-sided NMR system would predict IMF% in beef M. longissimus thoracis et lumborum. Here the RMS error of the correlation was 1.58 % IMF% and R2 was 0.97. The long-term stability, high accuracy, and nondestructive nature make unilateral NMR devices ideal for applications in the red meat industry where IMF% contributes to product value.

Recent Applications of Unilateral NMR to Objects of Cultural Heritage

Although nuclear magnetic resonance (NMR) is recognized as a powerful tool in many areas of research, among the investigative techniques used in the field of cultural heritage its application is still largely unknown. One of the reasons for this is that artifacts are complex heterogeneous systems whose analysis requires a multi-disciplinary approach. In addition, major drawbacks in the analysis of objects belonging to cultural heritage are their limited quantity, number of samples collected from the artifact, and their immovability. Consequently, a methodological approach where non-destructive, and possibly non-invasive techniques are used, is advisable. In recent years, thanks to the development of portable instruments, there has been an increasing use of the NMR methodology in the cultural heritage field. The use of portable NMR has allowed us to study several materials in the cultural heritage, such as frescoes, stones, wood, paper, and paintings, to address the challenges in monitoring dampness in historical masonries, to evaluate the penetration depth of a hydrophobic treatment into a porous material, and to study of the effect of cleaning procedures on artifacts. In this paper, recent studies illustrating the potential of NMR portable methodologies in this field of research are reported.

A Novel Design of a Unilateral Nuclear Magnetic Resonance Sensor for Soil Moisture Detection Based on a Simplified Analytical Model

A Novel Design of a Unilateral Nuclear Magnetic Resonance Sensor for Soil Moisture Detection Based on a Simplified Analytical Model

Cleaner Leather Tanning and Post-Tanning Processes Using Oxidized Alginate as Biodegradable Tanning Agent and Nano-Hydroxyapatite as Potential Flame Retardant.

In this study, sodium alginate (SA) was oxidized with potassium periodate to produce an alginate-based tanning agent. Using OSA as a biodegradable tanning agent and a nano-hydroxyapatite (nano-HAp) low concentration suspension to give flame retardancy to leather, eco-design concepts were applied to establish a chrome-, aldehyde-, and phenol-free tanning process. Micro-DSC, 1H unilateral nuclear magnetic resonance (NMR), attenuated total reflection mode Fourier transform infrared spectroscopy (FTIR-ATR), and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) were used to investigate the complex matrix collagen-OSA-nano-HAp. Micro-differential scanning calorimetry (micro-DSC) was used to assess OSA's ability to interact with collagen and stabilize the collagen-OSA matrix, while 1H unilateral (NMR) was used to investigate the aqueous environment and its limitations around collagen molecules caused by their association with OSA and nano-HAp. Industrial standard tests were used to assess the mechanical properties and fire resistance of the new leather prototype. The findings reported here indicate that both OSA and nano-HAp are suitable alternatives for cleaner tanning technologies and more sustainable leather.

Damage and restoration of historical urban walls: literature review and case of studies

Within this work, the causes of collapses and damages occurred in masonry artefacts have been evaluated to properly identify suitable monitoring and restoration methods. In this regard, a comprehensive literature review has been performed. Based on the results, the moisture has found to be a critical parameter, which affects the structural health of masonry artefacts. Diverse non-destructive methods were employed to measure the moisture and monitor the materials involved: the Infrared Thermography, the Electrical Resistivity Tomography and the Ground Penetrating Radar, the Laser Scanning and Digital Terrestrial Photogrammetry, the Global Navigation Satellite Systems, the Unilateral Nuclear Magnetic Resonance, the Laser-Induced Fluorescence technique, the Acoustic Imaging and the Acoustic Tomography, the Geographic Information System and on-site survey process as well as computer modeling of the structure with specific FEM software. Finally, the implementation of tie-beams, Fiber Reinforced Polymers layers, ventilation, draining systems, and high-quality materials are proposed as solutions for controlling the moisture effect and retrofitting.

Ringing cancellation in Carr-Purcell-Meiboom-Gill-type sequences

We propose a four-step phase cycling scheme that can cancel ringings from both the excitation and the refocusing pulses in Carr-Purcell-Meiboom-Gill (CPMG) measurements. It allows accurate measurements of the first echo with short echo spacing tE, yielding improved precision of porosity, permeability, and fluid type identification in porous media study, at a cost of ∼25% signal reduction. In our example, we achieved tE = 100 μs on a 6.8 MHz unilateral NMR sensor without using a Q-switch. These methods can be integrated in all nuclear magnetic resonance (NMR) protocols using CPMG, such as relaxation (T1, T2) and diffusion measurements, and do not require additional hardware (e.g., Q-switches) to cancel ringing (although it can be used with a Q-switch to further reduce residual ringing).

Studies of periodic seawater spray icing with unilateral NMR

Sea water ice has a complicated pore structure consisting of brine-filled pockets within a solid ice matrix. In this work, an unilateral Nuclear Magnetic Resonance instrument was used to characterize the evolution of sea-ice brine inclusions in two types of ice: stationary seawater ice and seawater spray ice formed by periodic spraying on horizontal and vertical surfaces. The portable unilateral NMR was capable of measuring very low amounts of brine (<10% of the water-filled volume). CPMG experiments were performed to extract the information on brine content and T2 distribution at temperatures between −6 °C and −16 °C. 1D imaging was used to spatially resolve the ice brine accumulation. The results show that the seawater spray ice growth, brine content (greater for the horizontal orientation than for the vertical one), and T2 distribution (unimodal for stationary ice and bimodal for spray ice) depend on temperature and surface orientation.

Moisture Damage in Ancient Masonry: A Multidisciplinary Approach for In Situ Diagnostics

San Nicola in Carcere, one of the minor basilicas in the historical center of Rome, was the location of a wide investigation campaign of the water-related deterioration causes, present in the lower sector of the apse and adjacent pillars, affected by water infiltrations, mould and salt efflorescence. The results obtained identify the presence of water content and related effects mainly on the sides of the apsidal wall. This work focuses on the use of five Non-Destructive Techniques (NDT) and intends to show the gains obtained by integrating widely interdisciplinary methods, namely the Infrared Thermography (IRT), the Unilateral Nuclear Magnetic Resonance (Unilateral NMR), the Acoustic Tomography (AT), the Acoustic Imaging (AI) and the Laser-Induced Fluorescence (LIF). All the techniques contribute to the rapid, non-invasive and early identification of the moisture distribution, while some of them (LIF and AI) also address the determination of some moisture effects. The integrated use of different techniques helps to take the multidisciplinary point of view necessary to formulate an effective restoration intervention based on a sound scientific rationale; nonetheless, it allows to experiment a holistic approach, verifying the potential of a wide range of NDTs available within the context of a restoration yard.

Nano- to microscale three-dimensional morphology relevant to transport properties in reactive porous composite paint films

The quantitative evaluation of the three-dimensional (3D) morphology of porous composite materials is important for understanding mass transport phenomena, which further impact their functionalities and durability. Reactive porous paint materials are composites in nature and widely used in arts and technological applications. In artistic oil paintings, ambient moisture and water and organic solvents used in conservation treatments are known to trigger multiple physical and chemical degradation processes; however, there is no complete physical model that can quantitatively describe their transport in the paint films. In the present study, model oil paints with lead white (2PbCO3·Pb(OH)2) and zinc white (ZnO) pigments, which are frequently found in artistic oil paintings and are associated with the widespread heavy metal soap deterioration, were studied using synchrotron X-ray nano-tomography and unilateral nuclear magnetic resonance. This study aims to establish a relationship among the paints’ compositions, the 3D morphological properties and degradation. This connection is crucial for establishing reliable models that can predict transport properties of solvents used in conservation treatments and of species involved in deterioration reactions, such as soap formation.

Unilateral low-field magnetic resonance measurements of carbonation depth in unsaturated and saturated Portland cement mortars

Unilateral Nuclear Magnetic Resonance is used to characterize the carbonation depth in 0.60 w/c ratio unsaturated/saturated Portland cement mortars. A three-magnet array combined with a surface elliptical coil was utilized to obtain the Nuclear Magnetic Resonance signal at different positions along mortar samples. The T2 lifetime and signal intensity behaviors in the carbonated and non-carbonated zones were analyzed. Scanning Electron Microscopy images were used to identify the macro-porosity and micro-cracking in the samples. Results confirmed that the crossover point between profiles of T2 lifetime and signal intensity agree with the carbonation depth obtained by the phenolphthalein test. The carbonation depth at the position where the T2 lifetime begins to behave nearly constant is about 1.44 times the depth indicated by the phenolphthalein test. The spatial resolution was improved four times in comparison with previous research. Scanning Electron Microscopy images analysis confirmed a significant decrease in local porosity and crack area in the carbonated zone.

Profiles of paint layer samples obtained in the fringe field of a high field magnet by means of very short broadband frequency-modulated pulses.

In this article, we describe the acquisition of depth profiles, in particular of paint layers, in the static gradient of a high field magnet, providing a superior sensitivity. The main objective are reference profiles that help to understand scans made with noninvasive unilateral nuclear magnetic resonance (NMR), which often suffers from poor signal-to-noise ratio when working with real samples. Various technical aspects like the coil geometry and the limit of resolution are investigated. A major advancement is the use of frequency-modulated pulses that are very broadband and at the same time very short (25 μs). The latter is necessary to allow the acquisition of a CPMG echo train of old, rigid paint material. Despite being far from adiabatic, they provide uniform excitation and refocusing over 1 MHz, which corresponds to about 400 μm with the used gradient. We show that the uniformity is even sufficient to obtain biexponential relaxation profiles. With these tools, a paint sample from a restoration campaign is analyzed with different contrast criteria: The original and two layers from former restoration attempts can be visualized, and furthermore, the relaxation profiles allow to study the migration of plasticizing molecules.

Detection of acidic paper recovery after alkaline nanoparticle treatment by 2D NMR relaxometry.

Cellulose-based artefacts are highly prone to degradation, especially in the presence of acidic compounds, which trigger the depolymerization of cellulose chains and lead to a loss in the original mechanical resistance of the material. Calcium hydroxide nanoparticles dispersed in organic solvent have been recently proposed for the deacidification of cellulose-based artworks. In this work, changes induced on paper by a deacidification treatment, following an acidification bath, were studied by nuclear magnetic resonance (NMR) relaxometry and by the so-called NMR diffraction of water trapped in the cellulose network. The deacidification treatment modifies intrachain and interchain bonds in hydrolyzed and degraded cellulose, leading to a buffered cellulose network configuration, which is similar to that characterizing the untreated reference sample in terms of relaxation parameters. Overall, calcium hydroxide nanoparticles are demonstrated effective in hindering the degradation of cellulose induced by acids and ageing in strong environmental conditions, even from the standpoint of cellulose network arrangement. It is worth noting, too, that the unilateral NMR device used for the relaxation measurements may represent a powerful tool for the preservation of cellulose-based artworks because it allows for the monitoring of the conservation status of cellulose in a completely non-invasive manner.

Nondestructive quantification of moisture in powdered low-rank coal by a unilateral nuclear magnetic resonance scanner

ABSTRACT Moisture content in coal powder is a critical index because it controls the difficulty of coal handling and ultimately its combustion efficiency in coal-fired power plants. A unilateral proton nuclear magnetic resonance (NMR) scanner was applied in a laboratory to nondestructively quantify moisture content in powdered samples of brown and subbituminous coals. Due to the open geometry of the sensor unit, the scanner allows the nondestructive moisture quantification of a portion several millimeters below the surface of a large sample. Proton transverse relaxation was measured by the unilateral NMR scanner, and obtained moisture content values were compared with those by a conventional bilateral NMR apparatus. The comparison showed reasonable agreement with a root mean square residual of 4.1 wt.%H2O for a moisture content range of > 12 wt.%H2O (wet basis). This moisture-quantification performance by unilateral NMR is sufficient for the quality control of wet coal having a critical value of approximately 30 wt.%H2O in terms of the handling property (flow-ability). Because unilateral NMR requires no specific sample preparation, such as sample insertion into tubes, the system is potentially applicable to in-situ nondestructive monitoring of the coal moisture in power plants to contribute to improved efficiency of handling and combustion.

The Research on Corona Aging Silicone Rubber Materials’ NMR Characteristics

Nuclear Magnetic Resonance (NMR) detection is a non-destructive testing method that can be used to detect the aging state of organic materials. A unilateral NMR sensor is used in this study to detect the aging state of the corona aging samples of silicone rubber materials after 100-hour’s corona aging under different humidity. At the same time, a comparative analysis is made between the NMR results and the conventional methods results such as Fourier Transform Infrared Spectroscopy (FTIR) and static contact angle test. The results show that with the effect of corona discharge, the polymer structure of the silicone rubber materials change to a certain extent. These changes are shown as the effective transverse relaxation time $T_{\mathrm {2eff}}$ of aged sample decreases in the NMR detection. The results of NMR and FTIR both show that the molecular crosslinking density of silicon rubber materials increases, and the activity of the H-containing group decreases. With the increase of relative ambient humidity, $\Delta T_{\mathrm {2eff}}$ gradually increase, and it means the corona aging state is becoming much severer. The results of NMR are consistent with the results of FTIR and contact angle tests. The $T_{\mathrm {2eff}}$ of the same sample tested at different time does not have significantly changes. This indicates that the NMR characteristic of silicon rubber materials after corona are irreversible. The NMR method can test the permanent damage of silicon rubber materials caused by corona. Compared with the static contact angle test, the NMR method can analyze silicon rubber materials from the molecular structure level, and it has good portability and orientation. Meantime, NMR method can achieve a non-destructive aging state detection. Hence the NMR method will provide reference for the operation and maintenance of the silicone rubber composite insulator.

The effect of halloysite nanotubes dispersions on vegetable-tanned leather thermal stability

Leather artefacts in historical collections and old leather bookbindings in archives and libraries frequently show a variety of visible changes which alter their appearance and ability to be used, such as powdery surface, weakened structure, complete or partial loss of the grain layer. However, historical leather stabilization and consolidation yet represent a challenging problem for conservators due to the sensitivity of collagen to the action of most of the conservation and restoration formulations currently used. In this paper we report our recent research concerning the development of halloysite nanoparticles dispersions for enhancing the hydrothermal stability of weakened historical vegetable tanned leather. The effects of halloysite nanotubes (HNTs) dispersed in various aqueous and non-aqueous mediums on the thermal stability of collagen in historical leather were tested using thermal microscopy, thermogravimetry and micro differential scanning calorimetry. Unilateral nuclear magnetic resonance was used to evaluate the changes in water dynamics due to collagen matrix interaction with dispersion media. The treated samples were also characterized using infrared spectroscopy and scanning electron microscopy. The analytical assessment confirmed the leather thermal stability increase and a partial recovery of fibres cohesion, thus validating the use of HNT dispersions as a basic tool for the preservation of collagen-based materials. Further functionalisation and encapsulation using antimicrobials, fungicides and pH adjustment nanoparticles will deliver novel and more durable HNTs-based conservation treatments.

Pulsed magnetic field generation suited for low-field unilateral nuclear magnetic resonance systems

Pulsed magnetic fields can be used to provide instantaneous localized magnetic field variations. In presence of static fields, pulsed field variations are often used to apply torques and in-effect to measure behavior of magnetic moments in different states. In this work, the design and experimental performance of a pulsed magnetic field generator suited for low static field nuclear magnetic resonance (NMR) applications is presented. One of the challenges of low bias field NMR measurements is low signal to noise ratio due to the comparable nature of the bias field and the pulsed field. Therefore, a circuit is designed to apply pulsed currents through an inductive load, leading to generation of pulsed magnetic fields which can temporarily overpower the effect of the bias field on magnetic moments. The designed circuit will be tuned to operate at the precession frequency of 1H (protons) placed in a bias field produced by permanent magnets. The designed circuit parameters may be tuned to operate under different bias conditions. Therefore, low field NMR measurements can be performed for different bias fields. Circuit simulations were used to determine design parameters, corresponding experimental measurements will be presented in this work.

Nuclear magnetic resonance analysis for treatment decisions: The case of a white sculptural environment by Louise Nevelson

In this work both solid state nuclear magnetic resonance (NMR) and unilateral NMR have been applied to investigate the paint composition and to inform the treatment decision for a white sculptural environment by Louise Nevelson completed in 1977. Within ten years of installation, the sculpture required restoration and was repainted by a restorer. The restoration paint is currently stained, dirty and flaking. The original paint and the restoration paint composition were determined using solid state NMR. The original and the restoration paint were identified as an alkyd and a polyvinyl acetate paint, respectively. Pentaerythritol, a compound from the alkyd paint, was identified in the restoration layer and in some areas as a white powder on the surface of the sculpture. The original alkyd paint seemed to be in better condition than the restoration paint, suggesting that the migrated pentaerythritol had contributed to the degradation of the restoration layer. The free pentaerythritol may be a result of excess in the alkyd paint formulation rather than degradation of the original paint. The analytical study guided the decision to remove the highly degraded restoration paint. Cleaning systems using viscous carriers for the solvents were investigated and potential mechanical changes in the alkyd paint were evaluated using unilateral NMR.

Design and Experimental Implementation of a Low Frequency Pulsed Magnetic Field Generator

Pulsed magnetic field generation is a critical aspect of all nuclear magnetic resonance (NMR) experiments. In this paper, a novel design for a low field, low frequency (less than 5 MHz), pulsed magnetic field generation circuit suited for unilateral NMR applications is presented. A pulsed sinusoidal current is generated at an inductive load connected to an FET-based switch. The inductive load resonates at a frequency of approximately 2 MHz, which is also the precession frequency of $^{1}H$ protons in an external magnetic flux density of 500 G. The designed circuit can be tuned to operate at resonant frequencies of other chemical species as well. In this paper, the design parameters and operation of the prototype pulsed field generator will be discussed.

Increasing the detection distance of remote NMR using wireless inductive coupling coil

Unilateral nuclear magnetic resonance (UNMR) spectrometers have been applied in a variety of fields such as petrochemistry, materials science, and process control1. In UNMR measurements the sample is placed outside of the UNMR sensor and the signal intensity is reduced almost exponentially as the sample-to-sensor distances increases. To expand the detection limits of remote UNMR sensors, wireless inductive coupling was proposed and tested. This strategy was proved to reduce signal attenuation due to sample detachment from sensor, resulting in an increase in detection distance by one order of magnitude (i.e., from few millimeters to few centimeters). This novel approach broadens the potential applications of UNMR sensors and opens new opportunities in several areas, from chemical to biomedical applications.

In situ characterisation of readhesion treatments for ceiling paintings using unilateral NMR

Ceiling and wall paintings pose significant challenges for historic house management due to their position at the interface between the environment and the building. Tight restrictions to modifications on built heritage prevent total control of the environment, resulting in temperature and humidity fluctuations. Different hygrothermal responses within the wall painting stratigraphy frequently lead to fracturing and lifting of paint layers, necessitating remedial conservation to readhere areas of detachment. Assessing the success of readhesion interventions is difficult due to the hidden nature of the treatment and, often, limited access. This paper presents comparative results of two different adhesive treatments employed during the conservation of the baroque ceiling painting in the Queen's Staircase at Hampton Court Palace, analysed with unilateral nuclear magnetic resonance (NMR). This non-invasive technique enabled monitoring of the adhesive systems, based on Jun Funori and BEVA® 371 adhesives, up to a depth of 3,500 μm into the ceiling by providing specially resolved proton density profiles before and after treatment. The results offer a unique and pertinent assessment of treatment areas within a strictly limited timeframe. It is shown that the solvent carrier leaves the system within 24 hours and that the ultimate deposition of the adhesive can be identified.